1. Field of the Invention
This invention relates to electrical ceramic oxide devices. More specifically, it relates to electrical ceramic oxide devices having electrodes composed of ruthenium, iridium, osmium, or rhodium and the electrically conductive oxides of those metals. These electrodes make excellent contacts to electrical ceramic oxides, such as those used for ferroelectric capacitors for microelectronic memories, high temperature superconductors, and electro-optic devices.
2. Description of the Prior Art
Ruthenium has previously been used as an electrode material in electrolytic cells, as discussed in Thomas et al. (U.S. Pat. No. 4,507,183). Microelectronic applications of ruthenium, osmium, rhodium, and iridium as conductors and resistors are taught by Shibasaki (U.S. Pat. No. 4,227,039) and Schnable (U.S. Statutory Invention Reg. No. H546). Yoshida et al. recognized that because of their low resistivity the oxides of ruthenium, rhodium, palladium, rhenium, osmium, and iridium could function as cathode collectors in a solid electrolyte capacitor (U.S. Pat. No. 4,184,192). Yoshida et al. also disclosed that because of their resistivity and oxidizing power, the oxides of ruthenium, rhodium, rhenium, osmium, and iridium used as the electrolyte improved the performance of solid electrolyte capacitors (U.S. Pat. No. 4,186,423).
Recently, ruthenium oxide's electrical conductivity has led to its investigation as a reaction barrier between silicon and aluminum in integrated circuits. As a reaction barrier, it prevents degradation of electrical contacts caused by the solubility and diffusivity of silicon in aluminum. See Kolwa et al., "Microstructure of Reactively Sputtered Oxide Diffusion Barriers," 17 J. Elect. Materials 425 (1988); Krusin-Elbaum et al., "Characterization of Reactively Sputtered Ruthenium Dioxide for Very Large Scale Integrated Metallization," 50 Appl. Phys. Lett. 1879 (1987). The excellent adhesion of ruthenium oxide to silicon and silicon dioxide substrates is noted by Green et al., "Chemical Vapor Deposition of Ruthenium and Ruthenium Dioxide Films," 132 J. Electrochem. Soc. 2677 (1985).
A variety of electrical ceramic oxides exist, such as might be or are used as ferroelectric capacitors for microelectronic memories (for example, lead titanate, PbTiO.sub.3 ; lead zirconate titanate, "PZT"; lanthanum doped PZT, "PLZT"; and barium titanate, (BaTiO.sub.3)); electro-optic devices (for example, PLZT; lithium niobate, LiNbO.sub.3 ; and bismuth titanate, Bi.sub.4 Ti.sub.3 O.sub.12); and high temperature superconductors (for example, yttrium barium copper oxide, YBa.sub.2 Cu.sub.3 O.sub.7). The properties of these electrical ceramic oxides are typically optimized by heat treatments in oxidizing ambients at high temperatures (for example, 500 C. to 1100 C.). Many electrode materials which are commonly used in microelectronics and for other applications are not suitable for use under such conditions. As examples, aluminum melts or reacts with the electrical ceramic oxide material, while tungsten and molybdenum are destructively oxidized; silicides and polysilicon either react with the electrical ceramic oxides at the higher temperatures or are oxidized at the surface in contact with the electrical ceramic oxide.
Moreover, if the oxide of an electrode metal has a high resistivity, reaction of the electrode material with the electrical ceramic oxide will create an interfacial dielectric layer of oxidized electrode material between the electrode and the electrical ceramic oxide. This may give rise to a capacitor in series with the electrical ceramic oxide, reducing the voltage drop experienced across the electrical ceramic oxide. In the application of electrical ceramic oxides as ferroelectric capacitors for microelectronic memories, efficiency of storage is reduced as a result. Since the dielectric constants of ferroelectric capacitor materials are typically more than 10 times the dielectric constants of the non-ferroelectric interfacial layers which might be formed, the interfacial layer must be approximately 100 times thinner than the ferroelectric capacitor if 90% of the voltage applied to the capacitor is to be dropped across the ferroelectric capacitor. Since a thin film ferroelectric capacitor integrated into a microelectronic circuit has a typical thickness of 5000 .ANG., this requires an interfacial dielectric layer of oxidized electrode material of thickness less than 50 .ANG. (i.e. essentially no oxide). In the use of electrical ceramic oxide devices such as superconductors, the interfacial oxide inhibits ohmic conduction.
Thin ferroelectric ceramic oxide capacitors in integrated circuits or fabricated as test devices and investigated for circuit applications have used noble metals (e.g. platinum, palladium, and gold) as electrode materials in order to eliminate the problem of interfacial dielectric layers composed of the oxides of the electrode materials. However, noble metals have numerous disadvantages, including high cost, poor adhesion to silicon oxides, silicon nitrides, and ceramic oxides, and such high reactivity toward aluminum that the interconnection of capacitors utilizing noble metal electrodes with other circuit elements frequently requires the use of reaction barriers at all points where the aluminum interconnection makes contact to the electrodes of the capacitor.
Indium oxide and indium-tin oxide have also been used as electrode materials for thin film ferroelectric ceramic oxide capacitors. However, these compounds have insufficient conductivity to perform well as electrodes for such capacitors in integrated circuits, where it has always proved desirable to have conductive materials be as conductive as possible so that extended lengths can be used without causing significant voltage drops in the circuit.